magel



Aug. l1, 1959 T; T. MAGEL 2,899,297

METHOD OF PRODUCING DENSE CONSOLIDATED METALLIC REGULUS Filed April 19. l1949 y 2 Sheets-Sheet 1 WITNESSES.- L y. y nvm/TOR:

Z i I Theodore Tf Mage( M BY g55 METHOIDOF PRODUCING DENSE CONSOLI- DATED METALLIC REGULUS Application April 19, 1949, Serial No. 88,373' j r4k claims. (cr. '7s-84.1)

This invention relates to a method and apparatus for centrifugally casting metallic specimens. More particularly, itl relates toa methodV and apparatus.,forlreducing dense metal compositions while simultaneously separat; ing impurities from'the reduced dense metaland'ca'sting saidreduced, purified dense metal into well consolidated metal ingots'.

Inthef past, metallic specimens have beenreadily obtained from'the common ore-bearingrmaterials by refining methods of long commercial usage. These methods are quiterv acceptable` when large quantities of the raw materialA are available for processing, when `an-extremely High' yield is not desired, and when the finished metallic specimen is-not required to be completely homogeneous.

However, incertain specific cases as, for example, the use! off'ssile materials in neutronic'reactors,A neutron multiplying systems -and'other nuclear equipment, it is not only desirable-but essential that the metallic specim'en ofv fissionable material be completely free of all impuritieswand in a compacted, purifiedfstate; Under normal'labforatory conditions a sample may be repeatedly refined andfconcentratedso that a very pure-end product is obtained, butwith the disadvantage of aresultinglossI of` the yield.` These conditions are further complicated bythe fact `that relatively limited amounts of the rawore-bearing materials are available and thus kdo not lericiY themselvesreadily to a: mass'purification' scheme. Fur'- thermore, whileit is relatively easy. toprepare the finelydivided metal by la reducingV action of alkali metals ori alkaline earth metals on the'metal halides, itfis veryv diflcultfto prepare the'reducedmetal inv theformof'a" purified, well consolidatedregulusby `any methodheretofore known. y

, It is therefore, an'object of this' inventionito provide arapid, ei'cient method for preparing substantially pure metal fromlta compoundiof 'a dense'rnet'al;

It i's another object of this invention-to provide. a rapid, eicientfmethod for preparing substantiallyrapurei metal from a dense metal halide;

It: iswanother object of this invention to provide ai method for reducing-a dense, radioactive." metal halide to the homogeneous metallic state and simultaneously cast-1 ing the reduced metal'into a consolidated button while separating impurities `from thefnretal.

It isA also objectV ofthis invention to=providean lalpparatusfor reducing small quantities of ame/[allie salt tothe'substantially pure metallic state.

Itrisfa further object of this inventionrtoprovidean apparatus for simultaneously reducing adense metallic compositionr toI the substantially pure metallic state, separating the pure-metal from;impuritieazandforming said*` pure-1 metal lintoI a :well consolidatedregulus;

- It is-vstill-fatfurther object offthis invention--to-provide aniapparatusfor reducing a dense radioactive metalhalide to the homogeneous metallic state and simultaneouslyl casting the=.reduced metal intov a well Aconsolidated ingot while separating),,impu-ritiesnfrom-the reduced metal;

Still further" objects will` becomeV apparent to thoser Patented Aug. 111959 skilled in theA art from the description and example which follow. Y

In accordance with the objects ofthe presentinvenl tion it has been found that a salt of a densemetal such as a halide ofthe `dense metal may be reduced to the pure metallic state by the method and apparatus of7V this invention.

It is to be pointedV out that the expression dense metal` as used in this specification may be definedas a metal'lraving fa density greater than 610k gramsper cubic" centimeter. Examples of such dense metalsare mangafnese, zirconium, lanthanum, neodymium, hafnium, thorium, uranium, plutonium, americium, curium, and the" like. v

The reduction is accomplished by`fh'eating'th`e dense metallic salt in the presence of a reducing agent,schi as yan alkali metal or alkaline earth metal in al bombtype reacting chamber, while applying centrifugal force on the reacting materials. Separation of themetal from impurities is accomplished essentially by the incorpora- -tion of a constricted passageway at the vertex of a conical reacting chamber which is in-direct communicationv with a collecting chamber. When a centrifugal force is ap'F plied to the molten metal and slag from the reduction in -a `direction collinear with the axis of Vthe constricted pass-age, the dense molten metal is forced therethrough while the less dense slag is retained withinthe reacting chamber, resulting in asimultaneous separation of the reduced moltenVV metal from the slag and a compacting of said reduced metal into -a homogeneous mass. l

Before furtherl disclosing the nature and advantages ofl this invention, reference shouldbe made to the attached drawings hereby made a part of this specification. vIn the drawings like parts are identified' by the same reference numbers. Y f

Figure 1Vv is a sectional view inelevation of 'the cen. trifugal purification andV casting apparatus, andthe inw duction furnace. v

Figure 2Y is an enlarged sectional view in elevationY of4 the steel reaction bomb containing the. cone-shapedref Y action Crucible andshows the constricted'portion whichcommunicatesvwith the collection chamber dcednietl. I i

With reference to Figure l, vthere is shown-a grap el rotor`assembly 20,(support'ed`b`y graphit'eshaft 1.2,`A maintained'in the proper align-mentby. meansofwaterV cooled bearingl I6. Rotor' 20 is positionedcentiallyin the refractory heating chamber 13'4 and'is heatedby. in. ductive heating means 14" placed ,adjacent to' asbestos, insulation I'S'Surrounding tire exteriorfof said' chamber` 13. A twolpiece' refractoryl lid'l'S', through which passes theV upper'portion of shaft' 12', covers 4andfa'idsl the ret'en; tion of heat within the container 13. Not shown is a conventional 'means for introd'cin'g' rotational motion into rotor 20 through connecting slot 17`in'shaft' lf2;

A plurality of rectangular recesses are constructedin.. diametricallyV opposing@ pairs" into the upper face' ofroto r" ZiltoV hold theVY steelbombs llll Thev recesses have` the.' form of'rectangular' parallelpipeds'with five'sides -bc'iuntletfV by faces ofthe. rotor material andthe sixth open'. The'Y long axesV offthe recesses are perpendicular-to the axis of rotation of the rotor 20. The' steel reaction bombs', 11`are placedin theA recesses in suchga manner'thatthe" apices of the crucibles'extend radiallyoutwardifromtlie axis' of rotation of' shaft 1'2.v The` bombljfl is" heldinoperatin'g position by tamping apowdered refactoiy material'19such asmagnesium oxide into the space'belf tween the'rotor zirand'bomb rrsotha't -tii'eisteel boinl 11' does notlcon'tactany portion ofthegrapliite r'ot'orZfflI, This a'r'rangernent'effectively prevents theredction ofthef fr die. ref- Y steelbytrre' graphite 'atihigirtempemtiires.A

place in the recess of rotor 20. The outer case 21 of the bomb is machined from cylindrical solid steel stock to hold the cone-shaped beryllium oxide liner 22 into which the V,charge and reducing agent are placed. A cylindrical collection chamber 26, into which is fitted aY cup-shaped refractory liner 28 of beryllium oxide, extends outwardly from the cone-shaped refractory liner 22 and communicates with it by means of a constricted passageway 25 at the apex of said cone-shaped refractory liner 22. A beveled, circular beryllium oxide plug 24 is inserted into the liner 22 and is covered by an additional refractory cap 23.` The steel bomb cover Z7 cornpletes the assembly and is seated upon the refractory cap 23 and welded to the open end of the outer case 21. The entire assemblyis then placed in a recessof the graphite rotor 20 and surrounded by rmly tamped refractoryoxide 19.

g In the preferred practice of this invention the metallic salt to be reduced to the metal is one comprising a halide of a rare refractory metal consisting of zirconium, hafnium, thorium, uranium, plutonium, americium, curium and the like, and preferably the halide isV one comprising a chloride of the aforementioned metals. This method4 is particularly applicable to the preparation of one-gram quantities of the said dense metals although it is to be understood that no restriction is intended to be placed on the order of the size of preparation and purification of the metallic specimen. Somewhat larger and smaller samples have been successfully prepared by this method.

A description of the loading and assembly of the bomb is hereby presented for the purpose of illustrating the facility of operation of the machine and process.

A reducing agent and a halide of the metal to be reduced are placed in the conical reaction chamber defined by the refractory liner 22.

that the two components are not mixed nor disturbed in any manner until processing is begun. The berylliumV oxide plug 24 is inserted in the opening of liner 22,.the

refractory cap 23 is placed in position and the assembly is4 inserted into the machined steel outer case 21 of the bomb. The circular refractory spacer of beryllium oxide 23 is interposed between the crucible assembly and the steel bomb cover 25 prior to welding said steel cover to the bomb, and serves to protect the crucible and its contents from the uneven, heterogeneous heat from the following welding operation, and reduces the probability of a premature and incomplete reaction. The steel bomb cover 27 is attached to the case 21 by welding or any well known means to obtain a gas tight seal.

The sealed bomb is then placed in the recess of the rotor 20 in such a manner that the sealed end is nearest the shaft 12 While the vertex of the conical liner within the bomb extends toward the rim of the rotor. A refractory material such as powdered magnesium oxide is used as a packing material 19 surrounding the sealed bomb in the recess to prevent attack on the steel case at high temperatures by the graphite.

While it is desirable that a multiplicity of specimens be processed simultaneously, a single sample may be centrifuged provided a counterweight such as a dummy bomb or the like is employed in the opposite recess. It can also be seen that while a rotor with two recesses may be used, it is advantageous to employ a rotor having four recesses, as such a rotor permits the processing of a single sample, or, by use of the appropriate counterweights, any one of two, three or four samples.

Forming consolidated metal buttons by this method from a salt of a rare refractory metal is very desirable in that the contamination of the metal by the slag formed during the reduction operation is substantially eliminated.

This is accomplished primarily by the incorporation of,

a constricted passageway at the vertex of the reaction chamber and in communication with the cup-shaped receptacle for collecting the metallic specimen. The di- The halide is above andV covering the reducing agent, with care being exercised` ameter of the constricted portion is of such a size that the centrifugal force produced by the rotation of the rotor assembly at the desired speed is sufticient to effect the flow of the molten high density metal through said constricted portion, but is insuicient to permit material flow of the low density slag, thus eicaciously producing a homogeneous, consolidated metallic specimen. An aperture having a diameter of from 0.3 to 1.5 millimeters is satisfactory, while the preferred embodiment of the invention utilizes an aperture of about 0.5 millimeter.

The proportions of the reactants will, of necessity, depend on the nature of the materials used and the size of the apparatus. Normally in the practice of this invention samples in the quantity of about 1 gram are processed.

A specic example relative to the invention is hereby given in detail, but it is to be understood that this example is not intended to be limitingon the spirit or scope of the invention.

t Example In a conical reaction chamber dened by a beryllium oxide liner provided with a constricting passageway about 0.5 millimeter in diameter at the vertex conjoining an enlarged receiver are placed about 0.3 gram of calcium and about 1.5 grams of uranium trichloride in the order stated. The crucible is covered with a lid of magnesium oxide and an additional lid of beryllium oxide. The refractory liner containing the charge is then placed inside a steel bomb which is sealed by welding a steel cap to` the open end. The bomb and its contents are then placed in a recess in the graphite rotor so that the vertex of the bomb extends radially outward from the shaft of the rotor. The bomb is packed securely in the recess of the graphite rotor with magnesium oxide, a duplicate or dummy bomb is likewise packed in the opposite recess to maintain the balance of the rotor, and the entire rotor assembly is then placed in position within a high frequency induction furnace. The rotor is heated rapidly to 1400" C. by induction from a 50 kilowatt, 3000 cycle, 400 volt generator while rotating at a rate of speed sufficient to develop a force in the bomb of about fty times that of gravity. A speed of 900 revolutions per minute on a six inch rotor is suliicient to produce the necessary force. Heat is maintained for a period of time suicient to eifect complete reduction of the uranium trichloride to the metallic state, usually about two minutes. IAs reduction proceeds within the crucible, the dense, molten metal is thrown by centrifugal force tot ward the tip of the refractory conical liner, and passes be opened to obtain the dense metal specimen as a bright,

coherent regulus.

While only one example has been given, it should be pointed out that other reactants may be employed in the method of this invention. For example, lithium satisfactorily reduces plutonium fluoride in a minimum of about three minutes at 1100 C., e.g., 0.15 gram of lithium per 1.5 grams of plutonium tetrauoride. Double salts of the dense metals are easily subjected to reduction by the method of this invention. For example, anhydrous potassium thorium uoride (K2ThF6) may be reduced with metallic sodium to obtain thorium in the form of a coherent metal regulus, eg., 0.15 gram of sodium per 1.0 gram of potassium thorium fluoride at 1250 C. for at least two minutes.

Other reductants may be employed to reduce dense metal halides by the method of this invention. Any metal geweer ..11sed. All of the alkali metals and practically all of the alkaline earth metals will effectively reduce halides of the dense metals hereinbefore described, and combinav.tions of such reducing agents may also be employed in various proportions to obtain the metal in the desired elemental st'ate.

From the foregoing example and embodiments thereof, it will be seen that the apparatus and method of this invention offers numerous advantages in the preparation `iof small, coherent metallic specimens from dense metallic saltsV The metallic product is essentially purified from .the slag and other end products of the reaction, and is mail operation, including loading the crucibles, welding of the top to the bomb, reduction and cooling, requires about one hour. At the end of this time period, the

metallic specimen is ready for removal from the collecting chamber and after superficial cleaning may be put to .immediate use.

A further advantage of this method is the increase in the coherence of the metallic button, a substantial improvement over the other methods previously known.

Many embodiments of the invention are, of course, possible. The refractory crucible need not be of beryllium oxide, but may be of any refractory oxide which will withstand the temperatures used and will not contaminate 'the melt. For example, crucibles of aluminum oxide, calcium oxide or magnesium oxide may be used. While the preferred embodiment of the invention makes use of a conical reaction crucible, a hemispherical, pyramidal, or a like form may be satisfactorily employed.

The use of a lid of a fusible salt such as sodium chlovride placed directly over the charge in the reaction crucible aids in preventing any metal from sticking to the magnesium oxide lid, which often happens in the reduction of plutonium trichloride. The lid of sodium chloride melts as the temperature of the bomb increases to about 800 C; and any metal which may be thrown up to the lid falls back into lthe crucible and is combined with the major portion of the metal.

the bombs..

Since it is thus seen that many embodiments of th1s 'invention are possible, it is to be understood that the invention is not to be limited except as indicated in the appended claims.

What is claimed is: v

l. A method for obtaining a dense consolidated metallic regulus from a dense metal composition, which comprises providing at least two communicating zones, a rst zone for reducing the metal composition and a second zone for collecting reduced metal, a portion of the communication between said zones being constricted to provide resistance to the flow of low density materials but not suficiently constricted to prevent the ow of the high density molten metal product, heating the dense metal composition and reductant in said first zone to a temperature substantially above the melting point of the dense metal composition, and applying centrifugal force to said molten composition along an axis from the reaction zone through the constricted communication to the collecting zone so vas vto collect only dense metal product Vin the latter zone.

2. A method of obtaining a dense, consolidated metallic regulus from a dense metal composition, which comprises heating in a reacting zone a dense metal composition and a reducing agent to a temperature substantially' above the melting point of the higher melting reactant for a period of time sufficient to eiect reduction rof the dense metal' composition, applying centrifugal force to said reactants, said force being applied in a direction .along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the reduced Vmetal, continuing the application of said force while ythe rreduced'metal is cooling in the collecting zone and until said reduced metal is consolidated into a homogeneous,

coherent metal regulus in the latter zone.

3. A method of obtaining a dense, consolidated uranium regulus from a uranium salt, which comprises heating in a reacting zone a uranium salt and a reducing agent to a temperature substantially above the melting point of the higher melting reactant for a period of time sufficient to effect reduction of the uranium salt, applying centrifugal force to said reactants, said force being applied in a direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the uranium metal, continuing the application of said force while the uranium metal is cooling in the collecting zone and until said reduced metal is consolidated into a homogeneous, coherent uranium metal regulus in the latter zone.

4. A method of obtaining a dense, consolidated uranium regulus from a uranium halide, which comprises .heating in a reacting zone a uranium halide and :an alkaline earth metal to a temperature substantially `above the melting point of the higher melting reactant for a period of time sufficient to effect reduction of the uranium halide, applying centrifugal force to said reactants, said force being applied in a direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the uranium metal, continuing the application of said force while the uranium metal is cooling in the collecting zone and until said reduced metal is consolidated into a homogeneous, coherent uranium metal regulus in the latter Zone.

/ 5. A method of obtaining a dense, consolidated uranium regulus from a uranium chloride, which comprises heating in a reacting zone a uranium chloride and calcium metal to a temperature substantially above the melting point of the calcium metal for a period of time sucient to eect reduction of the uranium chloride, applying centrifugalforceV to said reactants, `said force being applied in a direction along an axis from the reacting .zone through a `constricted communication to a collecting zone, cooling the uranium metal, continuing the application of said force While the uranium metal is cooling in the collecting zone and until said reduced metal is consolidated into a homogeneous, coherent uranium metal regulus in the latter zone. v

6. A method for obtaining a dense, consolidated ur nium regulus from uranium -trichloride which comprises heating in a reacting zone 1.5 grams of uranium trichloride and 0.3 gram calciumv metal to a temperature of 1400 C. for at least two minutes, applying centrifugal force to the reactants, said force beingapplied in a `direction along lan axis from the reacting zone through a constricted communication to a collecting zone, cooling the reduced uranium metal, continuing the application of said force while the uranium metal is cooling in the collecting zone and until said uranium metal is consolidated into a homogeneous,coherent uranium metal regulus in the latter zone.

7. A method of obtaining a dense, consolidated thorium regulus from a thorium salt, which comprises heating in a reacting zone a thorium salt and a reducing agent to a temperature substantially above the melting A2 point of the higher melting reactant for a period of time suthcient to etect reduction of 4the thorium salt, apply- -ing centrifugal force to said reactants, lsaid force being applied in a direction along an axis from the reacting zone through a constricted communication to a p collecting zone, cooling the thorium metal, continuing the application of said force while the thorium metal is coolingin the collecting zone and until said reduced metal is consolidated into a homogeneous, coherent thorium metal regulus in the latter zone.

8. A method of obtaining a dense, consolidated thorium regulus from a thorium double salt, which comprises heating in a reacting zone a thorium double salt and an alkali metal to a temperature substantially above the melting point of the higher melting reactant for a period of time sutiicient to effect reduction of the thorium double salt, applying centrifugal force to said reactants, said force being :applied in a direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the thorium metal, continuing the application of said force While the `thorium metal is cooling in the collecting Zone and until said reduced metal is consolidated into a homogeneous, coherent thorium metal regulus in the latter zone.

9. A method of obtaining a dense, consolidated thorium regulus from an alkali metal thorium halide, which comprises heating in a reacting zone an alkali metal thorium halide and sodium to a temperature substantially above the melting point of the higher meltingreactant for a period of time sufficient to effect reduction of the alkali metal thorium halide, applying centrifugal force to said reactants, said force being applied in a direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the thorium metal, continuing the application of said force While the thorium metal is cooling in the collecting zone and until said reduced metal is consolidated into a homogeneous, coherent thorium metal regulus in the latter zone.

10. A method for obtaining a dense, consolidated thorium regulus from potassium thorium fluoride which comprises heating in a reacting zone 1.0 gram of potassium thorium tluoricle and 0.15 gram sodium metal to a temperature of 1250 C. for at least two minutes, ap-

plying centrifugal force to the reactants, said force being applied in a direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the reduced thorium metal, continuing the application of said force while the thorium metal is cooling in the collecting zone and until said thorium metal is consolidated into a homogeneous, coherent thorium metal regulus in the latter zone.

11. A method of obtaining a dense, consolidated plutonium regulus from a plutonium salt, which comprises heating in a reacting zone a plutonium salt land a reducing agent to a temperature substantially above the melting point of the higher melting reactant for a period of time sucient to eect reduction of the plutonium salt, applying centrifugal force to said reactants, said force being applied in a direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the plutonium metal, continuing the application of said'force while the plutonium metal is cooling in the collectingmzone anduntil said refducedk metal vis consolidated into a"homogeneou s, Acoherent plutonium metal regulus the latter zone. "3

l2. A method of obtaining a de'nse, consolidated plutonium regulus from a plutonium halide, which comprises heating in a reacting Zone a plutonium halide and an alkali metal to a temperature substantiallyrabove the melting point of the higher melting reactant for a period rot time sulcient` to etectreduction of the plutonium halide, applying centrifugal force to said reactants, said force being applied in a `direction along an axis from the reacting zone through a constricted communication to a collecting zone, cooling the plutonium metal, continuing the application of said force While the plutonium metal is cooling in the collecting Zone and until said Areduced metal is consolidated into Va homogeneous,

coherent plutonium metal regulus in the latter zone. 13. A method of obtaininga dense,` consolidated `plutonium regulus from a plutonium uoride, vvhich comprises heating in a reacting zone a plutonium uoride and lithium metal to a temperature'substantially above the melting point of the" lithium metal for a period of time suicient to effect reduction of the plutonium fluoride, applying centrifugal force to said reactants, said force being applied in a direction alongA an axis from the reacting zone through a constricted communication to a collecting zone, cooling the plutonium metal, continuing the application of said force While the" plutonium metal is cooling in the collecting zone and until said reduced metal is consolidated into a homogeneous, `coherent plutonium metal regulus in the latter zone.

14. A method for obtaining a dense, consolidated `plutonium regulus from plutonium tetrauoride `which comprises heating in a reacting zone 1.5 grams of plutonium tetrailuoride and 0.15 gram lithium metal to a temperature of 1100 C. for at least three minutes, `applying centrifugal force to the reactants, said force being applied in a direction along an axis from the reacting zone through a constricted communication to a collecting Zone, cooling the reduced plutonumimetal, `continuing the application of said force While `the pluto- ,nium metal is cooling in the collecting zone and until said plutonium metal is consolidated into a homogeneous, coherent plutonium metal regulus in the latter zone.

References Cited in the tile of this patent UNITED STATES PATENTS` 964,371 Bary July 12, 1910 1,212,426 Voigtlander et al Jan. `16, 1917 1,240,460 Knapp Sept. 18, 1917 1,378,189 Northrup n May 17, 1921 1,452,480 Patch Apr. 17, 1923 2,107,513 Swoger Feb. 8, 1938 `2,161,950 Christensen .lune 13, 1939 2,255,549 Kruh Sept.`9, 1941 2,378,042 Sorensen et al June 12, 1945 OTHER REFERENCES Goggin et al.: Metallic Uranium Industrial and Engineering Chemistry, vol. 18, pp. 114-116 (1926). 

1. A METHOD FOR OBTAINING A DENSE CONSOLIDATED METALLIC REGULUS FROM A DENSE METAL COMPOSITION, WHICH COMPRISES PROVIDING AT LEAST TWO COMMUNICATING ZONES, A FIRST ZONE FOR REDUCING THE METAL COMPOSITION AND A SECOND ZONE FOR COLLECTING REDUCED METAL, A PORTION OF THE COMMUNICATION BETWEEN SAID ZONES BEING CONSTRICTED TO PROVIDE RESISTANCE TO THE FLOW OF LOW DENSITY MATERIALS BUT NOT SUFFICIENTLY CONSTRICTED TO PREVENT THE FLOW OF THE HIGH DENSITY MOLTEN METAL PRODUCT, HEATING THE DENSE METAL COMPOSITION AND REDUCTANT IN SAID FIRST ZONE TO A TEMPERATURE SUBSTANTIALLY ABOVE THE MELTING POINT OF THE DENSE METAL COMPOSITION, AND APPLYING CENTRIFUGAL FORCE TO SAID MOLTEN COMPOSITION ALONG AN AXIS FROM THE REAC- 